Characterizing Complex Gas-Solid Interfaces with in Situ Spectroscopy: Oxygen Adsorption Behavior on Fe-N-C Catalysts

Electrocatalysts for the oxygen reduction reaction within polymer electrolyte membrane fuel cells based on iron, nitrogen, and carbon elements (Fe-N-C) have received significant research attention as they offer an inexpensive alternative to catalysts based on platinum-group metals. Although both the performance and the fundamental understanding of Fe-N-C catalysts have improved over the past decade, there remains a need to differentiate the relative activity of different active sites. Toward this goal, our study is focused on characterizing the interactions between O-2 and a set of five structurally different Fe-N-C materials. Detailed characterization of the Fe speciation was performed with Fe-57 Mossbauer spectroscopy and soft X-ray absorption spectroscopy of the Fe L-3,L-2-edge, whereas nitrogen chemical states were investigated with X-ray photoelectron spectroscopy (XPS). In addition to initial sXAS and XPS measurements performed in ultra-high vacuum (UHV), measurements were also performed (at the identical location) in an atmosphere of 100 mTorr of O-2 at 80 degrees C (O-2-rich). XPS and sXAS results reveal the presence of several types of FeNxCy adsorption sites. FeNxCy sites that are proposed as the most active ones do not show significant change (based on the techniques used in this study) when their environment is changed from UHV to O-2-rich. Correlation with Mossbauer and sXAS results suggests that this is most likely due to the persistence of strongly adsorbed O-2 molecules from their previous exposure to air. However, other species do show spectroscopic changes from UHV conditions to O-2-rich. This implies that these sites have a weaker interaction with O-2 that results in their desorption in vacuum conditions and re-adsorption when exposed to the O-2-rich environment. The nature of these weakly and strongly O-2-adsorbing FeNxCy sites is discussed in the context of different synthetic and processing parameters employed to fabricate each of these five Fe-N-C materials.